Process for preparing detergent compositions



PROCESS FOR PREPARING DETERGENT COMPOITIONS Edwin 0. Korpi and David D. 'Whyte, Cincinnati, Ohio,

assignors'to The Procter &Gamble'Cornpany, Cincinnati,- Ohio, a corporation of Ohio No Drawing. Application May 22, 1952, Serial No. 289,434

7 Claims. (Cl. 252-161) This invention relates toa process for preparing wetting, sudsing and detergent agents of the sulfated and sulfonated types.

More particularly this invention relates to a process for preparing wetting, sudsing and detergent agents in solid granular form which exhibit a markedly reduced tendency to cake or form lumps while in storage.

As used hereinafter, the term -sulfonation-is to be construed broadly to designate the reaction of organic materials with acidic sulfuric derivatives such as oleum, free S03, sulfuric acid, or mixtures of these, whether true sulfonates, sulfuric acid esters or mixtures of the two are produced .by the reaction. Also, the term sulfonate is meant 'to include sulfates, i. e., those compounds in which the sulfur atom is attached to the carbon atom through an oxygen atom, as well as the true sulfonates where the sulfur atom is attached directly to the carbon atom.

The production of the sulfonated type of synthetic detergent comprises, in general, mixing and reacting sulfonatable organic material with a convenient sulfonating agent such as sulfuric acid'of appropriate concentration and neutralizing the resulting acid mixture with an alkaline material. Neutralization may be accomplished with alkali hydroxides, alkaline salts, oxides or hydroxides of alkaline earths or heavy metals, ammonia or organic bases. For most purposes, the neutralizing'agent should be such as to form water-soluble salts of the sulfonated material, and sodium hydroxide or the alkaline salts thereof are commonly .used.

Inthe preparation of synthetic detergents iii-accordance with this procedure,'it is necessary to-employ a sulfonating agent in excess of the stoichiometric amount required to effect sulfonation in order to obtain a satisfactory .yield. Thus, a considerable excess of acid normally remains unreacted at the conclusion of the sulfonation step and this is eliminated in the subsequent steps of the process. This elimination is most simply accomplished by neutralization of the acid reaction mixture whereby the sulfonated compound is converted into a useful watersoluble salt and the excess acid is converted into sodium sulfate or other salt, depending upon the neutralizing agent used, of'relatively little value from the standpoint of detersive action. .It is one object of this invention to :provide means whereby *a portion of this excess of unreacted acid may be employed to incorporate into thereaction mixture an ingredient which will impart valuable properties to the ultimate detergent product.

Other materials are normally desirably present in such products :and among them might be mentioned .inor- .ganic builders :like the alkali metal phosphates (particularly the calcium sequestering phosphates), silicates and carbonates and organic additives like carboxymethyl cel- .lulose, higher fatty alcohols and "various amides. In ad- ..dition, perfumes are customarily added to such products and, optionally, fluorescent brightening agents. Theseingredients may be incorporated with the neutralizing agent or may be added to the neutralized reaction mix- 2,742,435 Patented Apr. 117, 1.956

ture. It is to be appreciated however that reasonable care must be exercised in the addition of 'these various compounds as is Well known in the art; e. g. the more volatile products would not be added prior to a high temperature spray-drying operation.

If the above described neutralization procedure is followed using an aqueous solution of sodium hydroxide'or a sodium salt as the neutralizing agent, a substantial percentage of the neutralized mixture comprises sodium sulfate. This salt contributes nothing of value to the finished product in the Way of detergency and in fact has been considered by some persons to have inherent disadvantages when present in products of this type.

In the production of the solid granular type of product with which We are here concerned, the neutralized reaction mixtures with the desired additives (necessary precautions regarding the additives being observed as hereinbefore mentioned) is subjected to a spray-drying operation as is well known in the art. Although methods used may vary somewhat in details, in a typical procedure of carrying out this operation, the desired mixture, in flowing condition, is pumped through a spray nozzle and thereby atomized into a chamber containing air which has been heated to a temperature in the range from about 220-500" F. to evaporate the moisture from the atomized particles. The air may pass either in concurrent or in countercurrent direction to the sprayed mixture and by regulation of the height of the chamber and the temperature and velocity of air the drying of the particles can be substantially completed before they fall to the bottom of the chamber from which they are normally continuously removed.

It will be appreciated that although a spray-drying operation as hereinbefore described is'the method we normally prefer for producing a product of this type in particulate form, other methods such as, for example, drum drying or roll drying may also be used.

A number of synthetic detergent products exhibit the very undesirable tendency to lose their free-flowing'properties and cake or form lumps while in storage on the 'retailers shelves. This tendency is particularly apparent in those products containing an alkyl-aryl sulfonate, such as, for example, alkyl benzene sulfonate, as the active ingredient, whether the alkyl-aryl sulfonate comprises the sole active ingredient or is in admixture with various other types of synthetic organic detergents, the mixture comprising the active portion of the detergent product. This caking and lumping tendency is enhanced by the presence of heat and moisture and therefore such products tend to lose their free-flowing characteristics much more readily while in storage under conditions prevailing during the summer months.

It has been found that if a low molecular weight organic sulfate such as, for example, methyl sulfate, ethyl sulfate or isopropyl sulfate, normally in the form of the alkali metal salt, is incorporated in a product exhibiting the above described characteristics the tendency of the product to cake and form lumps is markedly reduced and it is an object of this invention to provide a means whereby such organic sulfate may be readily incorporated into such product. In addition, because a portion of the sodium sulfate is thus effectively replaced by such organic sulfate, the undesirable characteristics attributed to the presence of sodium sulfate are to that extent minimized.

We have discovered an improved process for preparing wetting, sudsing and detergent agents in solid granular form which exhibit a markedly reduced tendency to cake or form lumps while in storage and, for purposes of this application, those wetting, sudsing and detergent agents exhibitin such desirable characteristics will be referred to as agents having improved anti-caking propertics. This process comprises: sulfonating a high molecular weight alkylaryl compound, such as the alkyl benzenes, having at least eight carbon atoms in the alkyl chain, with an excess of a sulfonating agent such as oleum, free $03, sulfuric acid or mixtures of these; mixing the acid mixture from this reaction with a low molecular weight mono-hydroxy alcohol having from 1 to 6 carbon atoms wtereby residual sulfonating power of the excess acid remaining in the primary sulfonation acid mixture is utilized in sulfating such alcohol; neutralizing any spent acid remaining in the reaction mixture with an alkaline material and spraydrying to solid granular form an aqueous mixture containing said neutralized reaction products.

it is to be understood that the process may be carried out by either batch or continuous means and we have found that a convenient method of incorporating the low molecular weight alcohol sulfate into the product in a continuous manner is simply by injecting the alcohol into the line through which the acid mix from the primary sulfortation is passing.

Since it is known that in detergent products in small solid particle form which contain an alkyl aryl sulfonatc as the active ingredient, or as a portion of the active ingredients, the tendency to cake and form lumps is particularly apparent; and since it is also known that the incorporation of a low molecular weight alkyl sulfate into any product of this type which exhibits the calzing and lumping tendency will appreciably reduce such tendency and result in a product having improved anti-calLing properties; it is to be appreciated that our invention finds application not only to those products which are to contain an alkyl aryl sulfonate as the sole active ingredient but also to those products wherein the alkyl aryl sulfonate comprises only a portion of the active ingredients (e. g., products wherein the active ingredients comprise a mixture of an alkyl benzene sulfonate and an alltyl sulfate, the alkyl chains in each case containing from eight to about twenty-two carbon atoms.

The sult'onation of organic materials in. sequence (generally referred to as series sulfonation) is known (see, for example, U. S. 2,529,538 to R. A. Henry et al.) in all such previously described sequential sulfonation processes the normal procedure was to first sulfonate a high molecular weight organic material to give a reaction product having wetting, sudsing and detergent properties, and to then add to the acid reaction mix from this first sulfonation reaction another high molecular weight compound (i. e, one having 8 or more carbon atoms) which when sulfonated would also exhibit wetting, sudsing and detergent properties. Thus, a combination of two products. both having wetting, sudsing and detergent properties could be obtained. With all such processes, the high molecular Weight compound added to the acid reaction mix from the primary sulfonation had a relatively low reactivity and therefore, in order to obtain a reasonably good completeness of sulfonation of the secondarily added compound, a very large excess of sulfonating agent was necessarily employed in the primary sulfonation reaction to insure the presence of excess acid in the acid reaction mixture of sufficient strength to accomplish the secondary sulfonation. in actual practice, when such a sequential type of process was used, the desired degree of sult'onation of the secondarily added high molecular weight compound could seldom be obtained merely with the excess acid remaining in the primary sulfonatien acid reaction mix and the normal procedure was to add additional sulfohating agent to the primary reaction acid mix to ensure a practical completeness of the secondary sulfonation.

in contrast to the series sulronation process described in the above paragraph, and in accordance with our process, as described hereinbefore, the secondarily added compound, i. e. the low molecular weight monohydroxy alcohol, has a comparatively much higher degree of reactivity than those compounds suggested as secondary additives in the prior art and therefore is more easily sulfonated. Consequently, the strength of the excess acid in the primary acid reaction mix need not be of a high value to get a good completeness of reaction in the secondary sulfation. This in turn means that the amount of sulfonating agent added for the primary sulfonation reaction need normally only be sufiicient to give the optimum of completeness in that reaction. Furthermore, additional sulfonating agent need never be added to carry the secondary reaction to the desired degree of completeness since the strength of the excess acid in the primary acid reaction mix as hereinafter specified is suiiicient to give a relatively high completeness of sultation of the secondarily added alcohol in the amounts in which it is contemplated that such alcohol will be added. For example, with the series sulfation method, yields of from about 70% to of the desired low molecular weight alkyl sulfate are obtained. On the other hand, if the low molecular weight mono-hydroxy alcohol is present during the primary sulfonation step, yields of only about 30 to 40% of the low molecular weight organic sulfate may normally be expected. These latter mentioned low yields may be attributed to the extremely high reactivity of the low molecular weight alcohols and the consequent formation of over-sulfation products. Moreover, if the more reactive compounds were the first in order of sequence to be sulfated there would not only be the danger of over-sulfation because of the high strength of the sulfonating agent, but the concentration of the sulfonating agent would be reduced and an additional amount of the agent would very probably have to be added to carry the sulfonation of the then secondarily added high molecular weight compound to the proper completeness.

The product of the secondary sulfation, i. e. the low molecular weight alkyl sulfate, does not have any wetting, sudsing or detergent properties in itself but does impart to the final spray-dried granular product desirable characteristics in that it improves the anti-caking qualities of such product. Then too, when incorporated into the product in the manner suggested, it serves to replace a portion of the sodium sulfate normally found in such products without making it necessary to adjust and re-apportion the other materials going into the make-up of the final product and as a result, the formula of the crutcher mix prepared for a normal spray-drying operation need not be changed in order to maintain a predetermined active ingredient content in the product. Thus, as a practical matter, the low molecular weight alcohol actually serves as a neutralizing agent for a portion of the excess acid remaining in the primary acid reaction mix and to the best of applicants knowledge, a process of this type comprising: (1) the sulfonation of a high molecular weight organic compound to produce a product having wetting, sudsing and detergent properties, (2) neutralization of a portion of the excess acid in the acid reaction mix from this reaction by the addition thereto of a low molecular weight alcohol, the reaction product of this partial neutralization importing desirable properties to the final detergent product and (3) neutralization of the remaining spent acid with an alkaline material, has heretofore never been proposed.

In the sulfonation procedure herein described we have found that the concentration of the sulfonating agent as applied to the primary sulfonation, i. e. the sulfonation of the high molecular weight alkyl benzenes, is determined by the completeness of the sulfonation desired in this primary reaction. We normally prefer to use a sulfonating agent containing about 10-25% free S03 but these values are not to be considered limiting and other concentrations of sulfonating agent, e. g. those containing even free 803, may be used if desired.

prefer chiefly for this reason .not .to

.Thestr g h f the excess aci'clremainiug in .th acid reaction mix from the primarylsulfonation, whichiis to be utilized for the secondary suifonation, may range from about 90% to about 99% sulfuric acid.althoughjfor'best results itis desirably kept within the range from about 96% to 99%. Although theselimitsare notactually critical tothe operation, since some sulfonation 'canbe obtained with lower strength excess acid "for example, and withdue precautions a'higher acidstrength may be employed, they-are considered preferable for a number of considerations. The practicality of the operation is a primary factor among these considerationsand is-determinedlin part by sound economic practice. Also, if the excess acid strength is'higherthan about 99% sulfuric acid, the reaction must be very carefully controlled as regards time and temperature since because of the high reactivity of the low molecular weight compounds side reactions and over-sulfation are-easily promoted and undesirable products-may 'be *formed. .011 the other hand, if excess acid strength is -too'low an uneconomical yield of the sulfonated low molecularweig'ht compound may-be obtained.

The amount of excess acid present in relation to the amount of low molecular weight-alcohol added also does :not appear to be critical tothe secondarysulfationreaction. Although the reactionbetween the excess acid and ;the added low molecular weight alcohol is motouantitative andthis acid must necessarily be present in amounts greater-than the stoichiometric amount required to sulfate the low molecular weight .alcohol, :the amount of excess acid present in -the acid reaction mix :from the primary sulfonation is always .greatly .in excess .of the amount :normally required to sulfonate 'rto the .desired complete- ;ness :the low molecular weightalcohol inthe amounts in which such alcohol .is preferably :added.

Within the range of excess acid :strengths set forth above, temperature control is an important factor :and we have found that the temperature of ;the mixture :during the secondary sulfonation should not be.-allowed:to-rise substantially above 125. F. Temperatures .above :this

value promote the formation of undesirable products. The lower temperature limit is determined by practical .considerations such as, foriexample, solidification at .the lower temperatures of the stock being;sulfonated,;andzwe ture to drop much below about -,11,() F.

In addition, we have found that the length of time .the secondaryreactionis allowed to proceed also an important consideration and in; practice times of the order of 20 to 30 seconds have results.

It is to .be appreciated thatthe conditions of temperature, time, and the excess acid strength are all closely interrelated and that these various conditions-have to be balanced to obtain the desired end product insuitableyield. For example, with an excess acid strength-,of'about 99% sulfuric acid it is desirable that the reaction temperature be held at about 110 F. and that the reaction beallowed to proceed for only about 20-3D-seconds before the :acid reaction mixture is neutralized.

The quantity of the low molecular weight alcohol used may vary, but sufficient is normally addedto the primary sulfonation acid mix to give from about 2% to about 6% of low molecular weightalkyl sulfate in'the final'product. We prefer to use a maximum of about 6% but,"if desired, larger quantities, for example'up to about 10%, may be employed without undue adverse eflects. Amounts in ex cess of the 10% figure may be used but there-is no apparent advantage from using these greater amounts and in fact some undesirable effects, such as a decrease in detergency, have been noted when such larger quantities are incorporated in the product.

The method of determining the caking values of the various detergent products in small particle form is set :allow the :temperabeen :found to give satisfactory forth immediately below and the test is normally run under rather drastic conditions of temperature and "humidity whichpromote the tendency of the products to cake and'lump. This is to simulate the storagezconditions the product is subjected to while on the retailers shelves during the summer months. It is to be understood of .course that, Eif desired, other conditions of temperature and humidity may beused in the testing procedure.

Samples to :be tested are packaged asthey would be for normal retail use, i. e., invcartons whichlhave received -no special moisture-proofing treatment, and are then'placed in a cabinet in whichair'offixed-temperature and humid- -ity'(e. g. 90 at '80% relative =humidity-or .F. at 70% relative humidity) is .circulated. After :storage :for varying lengths of time, depending upon :the storage: conditions which are to besimulated,.the samples are. graded according to the ease .with which they pour .fromthe -earton, the amount ofzproducupresent in the form 'oflurnps and.theiamountofaproduct which1is hungmp on'the sides .(Oflllhfi carton. The samples may eitherbe-poured from the (carton by hand or, to eliminate the possibility of humanserror, by machine. The grading scale covers the range from 0 to 100, agradeof 0 representing a, product that cannot be removedfrom the carton without tearing the carton open and a grade of 100 representing a product that pours'like dry sand. The actual grade is the amount of theproduct in percent, based on the total amount of productin the box, which willpourroutand pass through a-wire screen having a A inch mesh.

In the following examples, which are not to be consideredlimiting but are merely to serve to more fully describe our invention, the caking values were determined .according totthe above describedmethod.

Example 1.A series of five samples of a spray-dried detergent product, the active ingredient of which was principally dodecyl benzene sulfonate, was prepared.

The alkyl 'benzene,',the major 'portion of "which was .dodecyl benzene was first sulfonated with oleum 'containing from "10 to 25% i'freeiSOs in a 'dominant'bath type of apparatus. The conditions of this primary *sulfonati'on reaction ;('as to time and temperature) were controlled so :as to give an excess acid strength inthe resulting acid reaction mixture .of from about 96-'99'% sulfuric acid. The secondary sulfation was then'accomplished'by injecting the low molecular weight alcohol into the line through which the acid reaction mix from the primary "sulfation was-passing. Three runs were madewith isopropyl alcohol as the low molecular weight alcohol added, the isopropyl alcohol being injected inamounts sufiicient to give concentrations of sodium .isopropyl sulfate in the finished product .eguivalent to respectively 2%, 4% and 7% by weightof the product. Also, one run each was made with methyl alcohol and ethyl alcohol as the secondary additives, the methyl and ethyl alcohol being injected in each case in an amount suflicient to give a concentration of sodium gmethyl sulfateor sodium ethyl sulfate in "the finished product equivalent to 4% by weight of the product. In all the secondary sulfonations the excess acid strength was of the order of 96-99% sulfuric acid, the reaction temperature was maintained below 12'5" F. and the time the reaction was allowed to proceed was of the order of 20 to B'Oseconds. Following the secondary-sulfonation reaction, any acid remaining in the mixture was neutralized by the addition of an aqueous solution of sodium hydroxide to the reaction mixtures. These neutralized mixtures were then mixed'with the desired additives and spray-dried to produce detergent product in small solid particle form. These products were then packed in paperboard cartons typically used for such a product, i. e., cartons which had received no special moisture-proofing treatment.

After-storage at F. and 80% relative humidity for varying lengths of time the cartons were opened and the caking-values of the various products were determined. The results appear in the table below.

It may be seen from the above data that the additive is very effective in inhibiting the caking tendencies of the detergent product and appears to be especially advantageous at and above the 4% usage level.

Example 2.--The procedure of Example 1 was followed to incorporate sodium isopropyl sulfate into an alkyl benzene type detergent, the alkyl chain of which contained an average of about 12 carbon atoms, with the exception that the caking determinations were made after storage of the samples at 80 F. and 70% relative humidity.

The results are tabulated below.

Table II Granule (Baking Grade Type and Amountof Additive At 6 At 12 At 20 At 26 days days days days None 88 71 69 2% Sodium Isopropyl Sulfate 82 46 32 4% Sodium Isopropyl Sulfate- 100 100 100 100 6% Sodium Isopropyl Suliate 100 100 99 99 Here again it may be seen that the caking inhibition is most pronounced when the additive is used in amounts equivalent to 4% or more by weight of the product.

Example 3 .-The procedure of Example 1 was followed to incorporate sodium methyl sulfate into a detergent product containing a mixture of 75% of an alkyl benzene sulfonate and 25% of an alkyl sulfate, the alkyl chain of which was obtained from the high molecular weight fatty alcohols derived from coconut oil, as the active ingredients.

Caking determinations were made after storage of the product samples at 90 F. and 80% relative humidity with the following results.

Table III Granule Caking Grade We claim:

1. A process for preparing wetting, sudsing and detergent agents having improved anti-caking properties when in small solid particle form which comprises sulfonating a material selected from the group consisting of high molecular weight alkyl-aryl compounds and mixtures of high molecular weight alkyl and alkyl-aryl compounds, all containing at least 8 carbon atoms in the alkyl chain, with a sulfonating agent selected from the group consisting of oleum, free S03, sulfuric acid and mixtures thereof, the amount of said sulfonating agent being sufficient to give the desired completeness of reaction and such that the acid mixture from the said sulfonation contains from about 90 to 99% strength sulfuric acid, thereafter admixing the said acid mixture with a low molecular weight monohydroxy alcohol having not more than 6 carbon atoms and effecting reaction between said alcohol and the excess acid in the said acid mixture, 7

allowing the reaction to proceed to substantial completeness without the formation of over-sulfation products, while restraining the temperature from rising substantially above 125 F'., whereby residual sulfonating power of the excess acid from the primary sulfonation reaction is utilized, the said'alcoholbeing added in an amount adequate to the formation upon sulfonation of an amount of lower alkyl sulfate sufficient to impart anti-caking properties to the final product, and thereafter substantially neutralizing anyremaining excess acid with an alkaline material and drying to solid granular form an aqueous mixture containing said reaction products.

, 2. A process for preparing wetting, sudsing and'detergent agents having improved anti-caking properties when in small solid particle form which comprises sulfonating a material selected from the group consisting of high molecular weight alkyl-aryl compounds and mixtures of high molecular weight alkyl and alkyl-aryl compounds, all containing at least 8 carbon atoms in the alkyl chain, with an amount of oleum, containing from 10% to 25 free sulfuric trioxide, sufficient to give the desired completeness of reaction and such that the acid mixture from the said sulfonation contains from about to 99% strength sulfuric acid, thereafter admixing the said acid mixture with a low molecular weight monohydroxy alcohol having not more than 6 carbon atoms and effecting reaction between said alcohol and the excess acid in the said acid mixture, allowing the reaction to proceed to substantial completeness without the formation of oversulfation products, while restraining the'tcmperatures from rising substantially above F., the said alcohol being added in an amount adequate to the formation upon sulfonation of an amount of lower alkyl sulfate, sufficient to impart .anti-caking properties to the final product, and thereafter neutralizing any remaining ex-v cess acid with an alkaline material and spray drying to solid granular form an aqueous mixture containing said reaction products. I

3. A process for preparing wetting, sudsing and detergent agents having improved anti-caking properties when in small solid particle form which comprises sulfonating a material selected from the group consisting of high molecular weight alkyl aryl compounds and mixtures of high molecular weight alkyl and alkyl-aryl compounds, all containing at least 8 carbon atoms in the alkyl chain, with a sulfonating agent selected from the group consisting of oleum, free $03, sulfuric acid and mixtures thereof, the amount of said sulfonating agent being sulficient to give 'the desired completeness of reaction and.

such that the acid mixture from thesaid sulfonation contains from about 90 to 99% strength sulfuric acid, thereafter admixing the said acid mixture with a low molecular weight monohydroxy alcohol having not more than 6 carbon atoms and effecting reaction between said alcohol and the excess acid in the said acid mixture, allowing the reaction to proceed to substantial completeness without the formation of over-sulfation products, while restraining the temperature from rising substantially above 125 F., the said alcohol being added in an amount sufficient to give from about 2% to about 6% of low molecular weight alkyl sulfate in the final product, and thereafter neutralizing the mixture with an alkaline material and spray drying to solid granular form an aqueousmixture containing said reaction products.

4. The process of claim 3 wherein the low molecular weight alcohol is methyl alcohol.

5. The process of claim 3 wherein the low molecular weight alcohol is ethyl alcohol.

6. The process of claim 3 wherein the low molecular weight alcohol is isopropyl alcohol. 7

7. A process for preparing wetting, sudsing and detergent agents having improved anti-caking properties when in small solid particle form which comprises sulfonating an alkyl-benzene having at least eight carbon atoms in the alkyl chain, with an amount of oleum suflicient to give the desired completeness of reaction and a resulting acid mixture of about 99% strength sulfuric acid, thereafter admixing the said acid mixture with methyl alcohol to effect reaction between said alcohol and said acid mixture while maintaining the temperature of the resultant mixture at about 110 F., the amount of alcohol added being suflicient to give an amount of methyl sulfate in the product equivalent to about 4% by Weight of the 10 product, allowing the reaction to proceed for 20 to 30 seconds and thereafter neutralizing any remaining excess acid with an alkaline material and spray-drying to solid granular form an aqueous mixture containing said reaction products.

References Cited in the file of this patent UNITED STATES PATENTS Re. 22,548 Brandt Sept. 26, 1944 2,249,317 Lieber July 15, 1941 2,268,140 Hengsterberg Dec. 30, 1941 2,529,539 Brod Nov. 14, 1950 2,631,980 Lewis Mar. 17, 1953 

1. A PROCESS FOR PREPARING WETTING, SUDSING AND DETERGENT AGENTS HAVING IMPROVED ANTI-CAKING PROPERTIES WHEN IN SMALL SOLID PARTICLE FORM WHICH COMPRISES SULFONATING A MATERIAL SELECTED FROM THE GROUP CONSISTING OF HIGH MOLECULAR WEIGHT ALKYL-ARYL COMPOUNDS AND MIXTURES OF HIGH MOLECULAR WEIGHT ALKYL AND ALKYL-ARYL COMPOUNDS, ALL CONTAINING AT LEAST 8 CARBON ATOMS IN THE ALKYL CHAIN, WITH A SULFONATING AGENT SELECTED FROM THE GROUP CONSISTING OF OLEUM, FREE SO3, SULFURIC ACID AND MIXTURES THEREOF, THE AMOUNT OF SAID SULFONATING AGENT BEING SUFFICIENT TO GIVE THE DESIRED COMPLETENESS OF REACTION AND SUCH THAT THE ACID MIXTURE FROM THE SAID SULFONATION CONTAINS FROM ABOUT 90 TO 99% STRENGTH SULFURIC ACID, THEREAFTER ADMIXING THE SAID ACID MIXTURE WITH A LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL HAVING NOT MORE THAN 6 CARBON ATOMS AND EFFECTING REACTION BETWEEN SAID ALCOHOL AND THE EXCESS ACID IN THE SAID ACID MIXTURE, ALLOWING THE REACTION TO PROCEED TO SUBSTANTIAL COMPLETENESS WITHOUT THE FORMATION OF OVER-SULFATION PRODUCTS, WHILE RESTRAINING THE TEMPERATURE FROM RISING SUBSTANTIALLY ABOVE 125* F., WHEREBY RESIDUAL SULFONATING POWER OF THE EXCESS ACID FROM THE PRIMARY SULFONATION REACTION IS UTILIZED, THE SAID ALCOHOL BEING ADDED IN AN AMOUNT ADEQUATE TO THE FORMATION UPON SULFONATION OF AN AMOUNT OF LOWER ALKYL SULFATE SUFFICEINT TO IMPART ANTI-CAKING PROPERTIES TO THE FINAL PRODUCT, AND THEREAFTER SUBSTANTIALLY NEUTRALIZING ANY REMAINING EXCESS ACID WITH AN ALKALINE MATERIAL AND DRYING TO SOLID GRANULAR FORM AN AQUEOUS MIXTURE CONTAINING SAID REACTION PRODUCTS. 